Process for conversion and hydrogenation of heavy petroleum oils and apparatus



PROCESS FOR CONVERSION AND HYDROGENATION OF HEAVY PETROLEUM OILS AND APPARATUS Filed Sept. 23, 1932 Jan. 28, 1936. R H. MOKEE NVENTOR ATTORNEY Patented Jan. 28, 1936 UNITED STATES PATENT OFFICE PROCESS FOR CONVE GEN AND APPARATUS Ralph E. McKee, New York,

ATION F HEAVY PETROLEUM RSION AND HYDRO- OILS N. Y., assignor to U. S. Hydro'ghe'nation Corporation, a corporation of Neva Application September 23, 1932, Serial No.

11 Claims. (Cl. 19653) The object of the present invention is to provide a method for the continuous conversion or crack- *'jronly\1nore diflicult to crack than the original oil,

but has 27 greatertendency. to deposit coke in the apparatus.

art to employ water vapor and catalyzing mediums in cracksame apparatus, re-crack the heavy oils for the production of more motor fuel.

oil, etc., gas and motor fuel, with the production of either A further object is to obtain a high recovery of low boiling-point hydrocarbons from crude pe troleum or other heavy liquid hydrocarbons by the simultaneous treatment of the latter, or of (obtained from such'heavy liquid petroleum by cracking), with steam and hydrogen preferably in the presence of a catalyzer.

at least, inconsiderable as compared with the pressures used in the so-called, Berginization of oil.

may, if desired, same type of construction as the lower coils. The middle coil 3 is for the simultaneous injection of the water which has been pre-heated in the upper coil and the pipe 20 to branch pipe 2| to an injector within the inlet end of vapor comes in the outlet end tains a catalyst 5.7:.

The outlet end of the secondary coil 6 communicates with a discharge pipe 25 which may vapors led through pipe 28 to the separating tank to enable through the-secondary coil. I1 desired, fresh oil may be admitted to the secondary "be heated to somewhat above coil through pipe 29 controlled by valve 3d, and heated water or steam admitted to the inlet oi? said secondary coil through pipe 3! controlled by valve 33. Also, hydrogen may be admitted to the inlet of the secondary coil'through pipe 3d controlled by valve 35.

Thecondenser 26 discharges through pipe 26a: into receiving tank 36, having a side gauge 37. Burner 1 may receive oil from any suitable source which may be blown with air to the burner, as by blower 3B driven by motor 39.

The oil and water are, thoroughly mixed by the injector or injectors at the point where the two are brought together. This gives rise to the formation of a spray of oil in an atmosphere oi steam if the water has been heated sufficiently, so that it either is steam, or breaks into steam at the time it passes through the injector. In case the water is only hot, but not above 212 F., there results an emulsion of oil and water due to the action of the injector in mixing the two products. This emulsion on reaching the heated coil 3 forms a spray of-oil in steam similar to that which would be formed if the water were heated to above 212 F. The resulting spray of oil in an atmosphere of-steam passes through the heatedcoil 3, which coil may 1000 F., and due to the simultaneous action of heat and steam, and also of a catalyzer 5 inserted into the latter part of the coil, will, by cracking of the heavy petroleum, produce a small amount of gas, (the amount depending on the temperature used) much motor fuel and some, say 30%, of the original volume of the oil, of a heavy residual oil.

The direction of the flow in the secondary coil is the reverse of that in the primary coil. This is in order that in the lower part of the secondary coil, the pipes which are nearest to the burner i will not be overheated. It also has secondary advantages in that, by such. treatment, the oil and water vapors which are passing through the coil will be kept as near as possible at the desired temperature for a longer period. The amount of oil passing through the secondary coil may be only one-fourth that passing through the primary coilLB. In other words, its speed through the coil will be less, though still having a high velocity. The .coil 6 may carry a catalyzer bx. p

The catalyzers 5, 5a: are inserted in the drawing as if in the last length of the primary and secondary coils. They can be placed in other lengths as well. They can be inserted by removal of the return bends 3x, Gas, on the left of the drawing by unscrewing the flanges indicated.

Any suitable hydrocarbon reactive catalyzer may be employed, and in the drawing, the catalyzers are shown of metallic mesh and they may comprise surfaces or solid bodies of metallic chromium, nickel, molybdenum oxide, tungsten oxide, and in some cases, other metallic oxides. The tubes themselves may be composed of a high nickel alloy such as chrome-nickel-steel tubes. The chromium and nickel are used as oatalyzers for the hydrogenation.

The returnbend and flanges indicated on the left side of the kiln can be readily opened up so that in case any one tube becomes injured or needs to be replaced, it may be removed and replaced with a new tube.

In order that heat may not be lost by the return bends which are outside of the kiln proper,

they may be within a casing 9, the doors indtcated at It in the drawing.

The seperating tank ll is provided to receive, preferably, the product from both the primary and secondary coils, though, if desired, a separate separating tank (not shown) may be used for the products from the secondary coil.

After tank it has been in use for a short period of time, it may be so hot due to the evolved steam and vapors of motor fueLthat it may distill over into the condenser products of so high a boiling point that they are useless for motor fuel or kerosene.- In such a case, it may be desirable to cool the separating tank, and for this purpose, water sprays are indicated at E2, so that, by

turning water upon them, this partial separation into heavy materials to be re-run through the secondary coil and vapor to pass through the condenser to give the desired motor fuel, may be controlled.

In the simultaneous cracking and hydrogenation of the petroleum, hydrogen may, with advantage, be injected along with water vapor and the oil to be cracked and hydrogenated. The steam under these conditions gives some nascent hydrogen, and additional hydrogen has advantages in increasing the speed of hydrogenation.

As hereinbefore'stated, hydrogen may be injected from tank I?! along with water and oil, into the secondary coil 6. It can also be injected if desired, into the primary coil at approximately the same point at which the water is injected.

While straight tubes connected by return headers are indicated, there may be substituted,

though less desirable, so-called coils made in feed of the materials in these spiral form. The coils may be either concurrent or countercurrent to the supply of heat My preference is that the materials to be heated be passed out from the primary coil through the hottest point of the coil. As to the secondary coil which handles and recracks the residual oil, my preference is for the materials being heated to pass out from the system through the part of the coil farthest from the burner. The aggregatelength of the coils will be determined by the diameters of the constituent pipes, and by the capacity desired. What is required is a certain time of heating. The higher the speed at which the vapors move through the tubes, the longer the tubes will need to be, or the larger the diameter the tubes will have to be, in order that the material will be given the necessary time while being heated. For example, the primary coil 3 shown in the drawing, may be sixty feet long and made of tubes having an internal diameter of about three inches. The .secondary coil 6 may be forty feet in lengthior the same sized tubes. With such length and diameters of the primary and secondary coils an initial run of East Texas crude will produce a synthetic gas oil rich in low boiling point hydrobarrel daily capacity, producing a high gasoline conversion in the first run and recycled residue from any class of crude charging stock the length of the primary coil may be approximately 600 feet with 3 inch internal diameter, and the secondary coil may be approximately 500 feet in length with the same internal diameter.

carbon. For a commercial standard unit of 1,000 i for the primary purpose of mingled oil and the lowest, i. e., the hottest coil, and will be about 900 coil.

part 01' the primary F. near the top of the portion of water. 200 F.

weight as compared with the weight of the cowater. The volume of hydrogen used will vary with arily used in the petroleum industry.

- In addition to being unsaturated, the motor fuel contains considerable quantities of ring series hydrocarbons.

consequently, a higher B. t. u. value than the gasolines commonly on the market. In view of the above, it may be used in high compression automobile engines in leaner mixtures than ordi- It is well known in the art that condensable vapor products from the cracking or conversion 1. A process of treating petroleum oilfor the conversion thereof into motor fuel, by hydrogenation below the saturation point, which comprises the kind of oil being' passing co-mingled petroleum oil and water through a primary conversion zone subjected to a er vapors of both conversion zones together from the separating zone, and recycling residues from heated secondary conversion zone.

2. A process of producing motor fuel in accord- 5. A process of producing motor fuel in accordance with claim 1 in which hydrogen is led into the primary and secondary conversion zones in volume approximately one-third volume of the Water vapor in said zones.

6. A process of producing motor fuel in accordance with claim 1 in which the reacting materials are subjected at the discharge end of each zone to the action of a catalyst of the hydrogenation type.

conversion zone subjected to heat and pressure below 20 atmospheres, passing the resulting vapor and entrained liquid products directly to a separating zone, leading the liquid from said separating zone directly to a secondary conversion zone subjected to higher heat and below that required to convert a substantial proportion of said liquid into fixed gas, leading the products from said secondary conversion zone to said separating zone, removing the light vapors of both conversion zones together from the separating zone and leading the liquid residue from the separating zone back to the secondary conversion zone with hydrogenous material, such as water, and as a step in the process subjecting the heat treated products to the action of a catalyzing agent of thehydrogenation type and to hydrogen passed into the secondary conversion zone.

8. Apparatus for producing hydrocarbons 01' low boiling point which comprises a heat chamber ha'ving a burner at its lower end, a primary conversion coil in said chamber at the upper portion thereof, means for injecting co-mingled oil and water into said primary conversion coil, a. separating and expanding chamber of controlled temperature having communication with the outlet end of the primary conversion coil, 2. secondary conversion coll disposed at the lower portion of the heated chamber and exposed to heat of greater intensity and having its outlet at the top, and itsinlet at the bottom, so that the outlet sections of the primary and secondary coils liev substantially in the same heat receiving zone within the heated chamber, catalyzing agents disposed within the outlet sections of the conversion coils, a how connection communicating the base of the separating chamber with the in-' let of the secondary conversion coil, means'for discharging from the secondary conversion coil into the separating chamber, and means for re moving from the separating and expanding chamber the lighter products received from said coils.

9. Apparatus for producing hydrocarbons of low boiling point which comprises a heat chamber, a primary conversion coil in said chamber at the upper portion thereof, means for injecting co-mingled oil and water into said primary conversion coil, a separating and expanding chamber having commimication with the outlet end of the primary conversion coil, a secondary conversion coil disposed at the portion of highest heat of the heated chamber and having its outlet at the top, and its inlet at the bottom, so that the outlet sections of the primary and secondary coils lie substantially in the same heat receiving zone within the heated chamber, a flow, connection communicating the base of the separating and expanding chamber with the inlet of the secondary conversion coil, means connecting the top of the separating and expanding chamber with the outlet of the secondary conversion coil whereby the vapors discharged from the latter are mixed in said chamber with the vapors from the primary conversion coil, and means for removing from the separating and expanding chamber the lighter products received from said coils.

10. Apparatus for producing hydrocarbons of low boiling point which comprises a heat chamber, a primary conversion coil said chamber at the upper portion thereof, 'means for injecting co-mingled oil and water into said primary'conversion'coil, a' separating and'expanding chamber having communication with the outlet end of the primary-conversion coil, a secondary conthe portion of the heated chamber receiving the highest heat and having its outlet at the top, and its inlet at the botso that the outlet sections of the primary and secondary coils lie substantially in the same heat receiving zone within the heated chamber, catalyzing agents disposed within the outlet sec tions of the conversion coils, a flow connection communicating the base of the separating and expanding chamber with the inlet of the secondary conversion coil, vapor discharge means connecting the separating and expanding chamber and the outlet of the secondary conversion coil, means for removing from the separating and ex= panding chamber the lighter products received from said coii, and means for injecting fresh oil and water within the inlet of the secondary conversion coil with the'liquid residue from the separating and expanding chamber.

version coil disposed at 11, Apparatus for producing hydrocarbonsot low boiling point which comprises a heat chamber, a heating means at the base of said chamber, a primary conversion coil in said chamber at the upper portion thereof, means for injecting comingled oil and water into said primary conversion coil, a separating and expanding chamber having communication with the outlet end of the primary conversion coil, a secondary conversion coil disposed at the lower portion of the heated chamber and having its outlet at the top, and its inlet at the bottom, so that the outlet sections of the primary and secondary coils lie substantially in the same heat receiving zone within the heated chamber, a flow connection communicating the base of the separating and expanding chamber with the inlet of the secondary conversion coil, means for discharging from the secondary conversion coil into the separating and expanding chamber, means for removing from the separating and expanding chamber the lighter products from said coils, means for injecting fresh oil and water within the inlet of the secondary conversion coil with the heavier products from. the separating and expanding chamber, and means for injecting hydrogen into the secondary coil with the liquid residuetrom the separating and expanding chamber.

RALPH H. MCKEE. 

